Use of dithiine-tetracarboximides for controlling phytopathogenic fungi

ABSTRACT

The present invention relates to the use of novel and of known dithiine-tetracarboximides for controlling phytopathogenic fungi, and to methods of controlling phytopathogenic fungi in plant protection, and to plant protection compositions comprising these dithiine-tetracarboximides.

The present invention relates to the use of novel and of knowndithiine-tetracarboximides for controlling phytopathogenic fungi, and tomethods of controlling phytopathogenic fungi in plant protection, and toplant protection compositions comprising thesedithiine-tetracarboximides.

Dithiine-tetracarboximides per se are already known. It is also knownthat these dithiine-tetracarboximides can be used as anthelminticsagainst internal parasites of animals, in particular nematodes, and thatthey have insecticidal activity (cf. U.S. Pat. No. 3,364,229).Furthermore, it is known that certain dithiine-tetracarboximides areantibacterially active and have a certain effect against mycosis inhumans (cf. Il Farmaco, 2005, 60, 944-947). Moreover, it is known thatdithiine-tetracarboximides can be employed as pigments inelectrophotographic photoreceptors or as colorants in varnishes andpolymers (cf. JP-A 10-251265, PL-B 143804).

Since the ecological and economical demands made on modern fungicideskeep getting more and more stringent, for example as regards thespectrum of action, toxicity, selectivity, application rate, formationof residues and advantageous production, and since furthermore forexample resistance problems may occur, there is a constant need todevelop novel fungicides which meet the abovementioned demands better,at least in some areas.

It has now been found that dithiine-tetracarboximides of the generalformula (I)

in which

-   R¹ and R² are identical or different and represent hydrogen,    C₁-C₈-alkyl which is optionally monosubstituted or polysubstituted    by halogen, —OR³, —COR⁴, or represent C₃-C₇-cycloalkyl which are    optionally monosubstituted or polysubstituted by halogen,    C₁-C₄-alkyl or C₁-C₄-haloalkyl, or represent aryl or    aryl-(C₁-C₄-alkyl), each of which is optionally monosubstituted or    polysubstituted by halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR⁴ or    sulphonylamino,-   R³ represents hydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or    represents aryl which is optionally monosubstituted or    polysubstituted by halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,-   R⁴ represents hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy,-   n represents 0 or 1    are highly suitable for controlling phytopathogenic fungi.

Dithiine-tetracarboximides of the formula (I) according to the inventionand, if appropriate, their salts are highly suitable for controllingphytopathogenic harmful fungi. The abovementioned compounds according tothe invention show mainly a fungicidal activity and can be used not onlyin plant protection, in the domestic and hygiene fields, but also in theprotection of materials.

Formula (I) provides a general definition of thedithiine-tetracarboximides which can be used in accordance with theinvention. Carboximides of the formula (I) in which the radicals havethe meanings hereinbelow can preferably be used.

-   R¹ and R² are preferably identical or different and preferably    represent hydrogen, or represent C₁-C₆-alkyl which is optionally    monosubstituted or polysubstituted by fluorine, chlorine, bromine,    —OR³, —COR⁴, or represent C₃-C₇-cycloalkyl which is optionally    monosubstituted or polysubstituted by chlorine, methyl or    trifluoromethyl, or represent phenyl or phenyl-(C₁-C₄-alkyl), each    of which is optionally monosubstituted or polysubstituted by    fluorine, chlorine, bromine, methyl, trifluoromethyl, —COR⁴,    sulphonylamino.-   R¹ and R² are especially preferably identical or different and    especially preferably represent hydrogen, or represent C₁-C₄-alkyl    which is optionally monosubstituted or polysubstituted by fluorine,    chlorine, hydroxyl, methoxy, ethoxy, methylcarbonyloxy, carboxyl, or    represent C₃-C₇-cycloalkyl which is optionally monosubstituted or    polysubstituted by chlorine, methyl or trifluoromethyl, or represent    phenyl, benzyl, 1-phenethyl, 2-phenethyl or 2-methyl-2-phenethyl,    each of which is optionally monosubstituted to trisubstituted by    fluorine, chlorine, bromine, methyl, trifluoromethyl, —COR⁴,    sulphonylamino.-   R¹ and R² are very especially preferably identical or different and    very especially preferably represent hydrogen, methyl, ethyl,    n-propyl, isopropyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, or    represent cyclopropyl or cyclohexyl, each of which is optionally    substituted by chlorine, methyl or trifluoromethyl.-   R¹ and R² particularly preferably simultaneously represent methyl.-   R³ preferably represents hydrogen, methyl, ethyl, methylcarbonyl,    ethylcarbonyl or represents phenyl which is optionally    monosubstituted or polysubstituted by fluorine, chlorine, methyl,    ethyl, n-propyl, isopropyl or trifluoromethyl.-   R³ especially preferably represents hydrogen, methyl, methylcarbonyl    or phenyl.-   R⁴ preferably represents hydroxyl, methyl, ethyl, methoxy or ethoxy.-   R⁴ especially preferably represents hydroxyl or methoxy.-   n preferably represents 0.-   n preferably also represents 1.-   n especially preferably represents 0.

The following compounds may be mentioned individually:

-   (1)    2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (2)    2,6-Diethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (3)    2,6-Dipropyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (4)    2,6-Di(propan-2-yl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (5)    2,6-Dicyclopropyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (6)    2,6-Bis(2,2,2-trifluoroethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (7)    2,6-Bis[1-(trifluoromethyl)cyclopropyl]-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (8)    1H,5H-[1,4]Dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (9)    2,6-Bis(3,5-dichlorophenyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (10)    2,6-Diphenyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (11)    2,6-Dibenzyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (12)    2,6-Bis(2-methoxyethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (13)    2,6-Bis(2-hydroxybutyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (14)    2,6-Bis(2-hydroxypropyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (15)    2,6-Bis(2-phenoxyethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (16)    2,6-Bis(2-ethoxyethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (17)    2,6-Bis(2-phenylpropan-2-yl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (18)    2,6-Bis(1-phenylethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (19)    2,6-Bis(2-methoxy-2-methylpropyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (20)    2,6-Di-tert-butyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (21)    (1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)diethane-2,1-diyl    diacetate-   (22)    4,4′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dibenzenesulphonamide-   (23)    2,2′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)diacetic    acid-   (24)    2,2′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dipropanoic    acid-   (25)    2,2′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dibutanoic    acid-   (26)    2,2′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dihexanoic    acid-   (27)    2,2′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)bis(3,3-dimethylbutanoic    acid)-   (28)    3,3′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dibutanoic    acid-   (29)    5,5′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dipentanoic    acid-   (30)    2,6-Bis[3-(trifluoromethyl)cyclohexyl]-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (31)    2,6-Bis[3-(trifluoromethyl)phenyl]-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (32)    2,2′-(1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)bis(3-phenyl-propanoic    acid)-   (33)    2,6-Bis(2-hydroxyethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (34)    2,6-Bis(2-hydroxy-2-methylpropyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (35)    (1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dibutane-1,2-diyl    diacetate-   (36)    (1,3,5,7-Tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dipropane-1,2-diyl    diacetate-   (37)    2,6-Bis(hydroxymethyl)-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (38)    2,6-Dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone    4-oxide-   (39)    2-Ethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone-   (40) Diethyl    2,2′-(1,3,5,7-tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-e]dipyrrole-2,6-diyl)di-hexanoate-   (41)    2-[2-(1-Ethoxy-1-oxobutan-2-yl)-1,3,5,7-tetraoxo-2,3,5,7-tetrahydro-1H,6H-[1,4]dithiino[2,3-c:5,6-c′]-dipyrrole-6-yl]butanoic    acid.

Compounds (1), (2) and (3) can be used with special preference.

Novel dithiine-tetracarboximides are those of the formula (I-a)

in which

-   R^(1a) and R^(2a) are identical or different and represent    C₁-C₈-alkyl which is monosubstituted or polysubstituted by fluorine,    —OR^(3a), —COR^(4a), or represent C₃-C₇-cycloalkyl which is    optionally monosubstituted or polysubstituted by halogen,    C₁-C₄-alkyl or C₁-C₄-haloalkyl, or represent aryl-(C₁-C₄-alkyl)    which is monosubstituted in the alkyl moiety by —COR^(4a),-   R^(3a) represents C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or represents    aryl which is optionally monosubstituted or polysubstituted by    halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl,-   R^(4a) represents hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy,-   r represents 0 or 1,    where R^(1a) and R^(2a) do not simultaneously represent    acetoxymethyl or methoxymethyl.-   R^(1a) and R^(2a) are preferably identical or different and    preferably represent C₁-C₆-alkyl which is monosubstituted or    polysubstituted by fluorine, —OR^(3a), —COR^(4a), or represent    C₃-C₇-cycloalkyl which is optionally monosubstituted or    polysubstituted by chlorine, methyl or trifluoromethyl, or represent    phenyl-(C₁-C₄-alkyl) which is monosubstituted in the alkyl moiety by    —COR^(4a).-   R^(1a) and R^(2a) are especially preferably identical or different    and especially preferably represent C₁-C₄-alkyl which is    monosubstituted or polysubstituted by fluorine, hydroxyl, methoxy,    ethoxy, methylcarbonyloxy, carboxyl, or represent C₃-C₇-cycloalkyl    which is optionally monosubstituted or polysubstituted by chlorine,    methyl or trifluoromethyl, or represent 1-phenethyl or 2-phenethyl,    each of which is monosubstituted in the alkyl moiety by —COR^(4a).-   R^(1a) and R^(2a) are very especially preferably identical or    different and very especially preferably represent    2,2-difluoroethyl, 2,2,2-trifluoroethyl, or represent cyclopropyl or    cyclohexyl, each of which is optionally substituted by chlorine,    methyl or trifluoromethyl.-   R^(3a) preferably represents methyl, ethyl, methylcarbonyl,    ethylcarbonyl, or represents phenyl which is optionally    monosubstituted or polysubstituted by fluorine, chlorine, methyl,    ethyl, n-propyl, isopropyl or trifluoromethyl.-   R^(3a) especially preferably represents methyl, methylcarbonyl or    phenyl.-   R^(4a) preferably represents hydroxyl, methyl, ethyl, methoxy or    ethoxy.-   R^(4a) especially preferably represents hydroxyl or methoxy.-   r preferably represents 0.-   r preferably also represents 1.-   r especially preferably represents 0.

Depending on the nature of the above-defined substituents, the compoundsof the formula (I) can have acidic or basic properties and can formsalts, if appropriate also internal salts, or adducts with inorganic ororganic acids or with bases or with metal ions.

Suitable metal ions are, in particular, the ions of the elements of thesecond main group, in particular calcium and magnesium, of the third andfourth main group, in particular aluminium, tin and lead, and of thefirst to eighth subgroup, in particular chromium, manganese, iron,cobalt, nickel, copper, zinc and others. Especially preferred are themetal ions of the elements of the fourth period. In this context, themetals can be present in the various valencies which they can assume.

If the compounds of the formula (I) have attached to them hydroxyl,carboxyl or other groups which induce acidic properties, these compoundscan be reacted with bases to give salts.

Examples of suitable bases are hydroxides, carbonates,hydrogencarbonates of the alkali and alkaline earth metals, inparticular those of sodium, potassium, magnesium and calcium,furthermore ammonia, primary, secondary and tertiary amines with(C₁-C₄—)-alkyl radicals, mono-, di- and trialkanolamines of(C₁-C₄)-alkanols, choline and chlorocholine.

If the compounds of the formula (I) have amino, alkylamino or othergroups which induce basic properties attached to them, then thesecompounds can be reacted with acids to give salts.

Examples of inorganic acids are hydrohalic acids such as hydrofluoricacid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulphuricacid, phosphoric acid and nitric acid, and acidic salts such as NaHSO₄and KHSO₄.

Organic acids are, for example, formic acid, carbonic acid and alkanoicacids such as acetic acid, trifluoroacetic acid, trichloroacetic acidand propionic acid, and also glycolic acid, thiocyanic acid, lacticacid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalicacid, alkylsulphonic acids (sulphonic acids with straight-chain orbranched alkyl radicals having 1 to 20 carbon atoms), arylsulphonicacids or -disulphonic acids (aromatic radicals, such as phenyl andnaphthyl, which have one or two sulphonyl groups attached to them),alkylphosphonic acids (phosphonic acids with straight-chain or branchedalkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids oraryldiphosphonic acids (aromatic radicals, such as phenyl and naphthyl,which have one or two phosphonic acid radicals attached to them), itbeing possible for the alkyl or aryl radicals to have attached to themfurther substituents, for example p-toluenesulphonic acid, salicylicacid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoicacid etc.

The salts which can thus be obtained also have fungicidal properties.

The dithiine-tetracarboximides of the formula (I) which can be used inaccordance with the invention can be prepared in a known manner (cf.U.S. Pat. No. 3,364,229, Synthetic Commun. 2006, 36, 3591-3597 and IlFarmaco 2005, 60, 944-947).

In a first process, for example (cf. Il Farmaco 2005, 60, 944-947),succinic anhydride of the formula (II) is reacted, in a first step, withan amine of the formula (III), if appropriate in the presence of adiluent. Thereafter, the resulting succinic monoamides of the formula(IV) are then reacted with a sulphur source (for example thionylchloride). Depending on the reaction conditions, thedithiine-diisoimides of the formula (V) can be isolated before they areconverted into the dithiine-tetracarboximides of the formula (I-b). Thepreparation of the dithiine-tetracarboximides of the formula (I) can beillustrated by the following scheme (in which R is R¹ or R²):

The dithiine-diisoimides of the formula (V)

in which R¹ and R² have the abovementioned meanings are also suitablefor controlling phytopathogenic fungi.

Here, R¹ and R² have the abovementioned preferred, especially preferred,very especially preferred or particularly preferred meanings.

Novel dithiine-diisoimides are those of the formula (V-a)

in which R^(1a) and R^(2a) have the abovementioned meanings.

R^(1a) and R^(2a) have the abovementioned preferred, especiallypreferred, very especially preferred or particularly preferred meanings.

In a second process, for example (cf. U.S. Pat. No. 3,364,229, SyntheticCommun. 2006, 36, 3591-3597), dichloromaleic anhydride, of the formula(VI), is reacted, in a first step, with an amine of the formula (III),if appropriate in the presence of a diluent. Thereafter, the resultingmaleic imides of the formula (VII) are then reacted with a sulphursource (for example hydrogen disulphide or thiourea). If appropriate,the resulting dithiine-tetracarboximides of the formula (I-b) cansubsequently be oxidized with nitric acid. The preparation of thedithiine-tetracarboximides of the formula (I) can be illustrated by thefollowing scheme (in which R is R¹ or R²):

The present invention furthermore relates to a plant protectioncomposition for controlling undesired fungi, comprising at least onedithiine-tetracarboximide of the formula (I) or a dithiine-diisoimide ofthe formula (V). These preferably take the form of fungicidalcompositions which comprise agriculturally useable adjuvants, solvents,carriers, surface-active substances or extenders.

Furthermore, the invention relates to a method of controlling undesiredmicroorganisms, characterized in that dithiine-tetracarboximides of theformula (I) or dithiine-diisoimides of the formula (V) are applied inaccordance with the invention to the phytopathogenic fungi and/or theirenvironment.

According to the invention, carrier is to be understood as meaning anatural or synthetic, organic or inorganic substance which is mixed orcombined with the active substances for better applicability, inparticular for application to plants or plant parts or seeds. Thecarrier, which may be solid or liquid, is generally inert and should besuitable for use in agriculture.

Suitable solid or liquid carriers are: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as finely divided silica, alumina and natural orsynthetic silicates, resins, waxes, solid fertilisers, water, alcohols,especially butanol, organic solvents, mineral and vegetable oils andderivatives of these. Mixtures of such carriers may also be used.Suitable carriers for granules are: for example crushed and fractionatednatural minerals, such as calcite, marble, pumice, sepiolite, dolomite,and also synthetic granules of inorganic and organic meals and alsogranules of organic material, such as sawdust, coconut shells, maizecobs and tobacco stalks.

Suitable liquefied gaseous extenders or carriers are liquids which aregaseous at ambient temperature and under atmospheric pressure, forexample aerosol propellants, such as halocarbons, and also butane,propane, nitrogen and carbon dioxide.

Tackifiers, such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules and latices, such as gumarabic, polyvinyl alcohol, polyvinyl acetate, or else naturalphospholipids, such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

If the extender used is water, it is also possible, for example, to useorganic solvents as auxiliary solvents. Suitable liquid solvents areessentially: aromatic compounds, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatic compounds or chlorinatedaliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes ormethylene chloride, aliphatic hydrocarbons, such as cyclohexane orparaffins, for example mineral oil fractions, mineral and vegetableoils, alcohols, such as butanol or glycol, and also ethers and estersthereof, ketones, such as acetone, methyl ethyl ketone, methyl isobutylketone or cyclohexanone, strongly polar solvents, such asdimethylformamide and dimethyl sulphoxide, and also water.

The compositions according to the invention may comprise additionalfurther components, such as, for example, surface-active substances.Suitable surface-active substances are emulsifiers and/or foam formers,dispersants or wetting agents having ionic or nonionic properties, ormixtures of these surface-active substances. Examples of these are saltsof polyacrylic acid, salts of lignosulphonic acid, salts ofphenolsulphonic acid or naphthalenesulphonic acid, polycondensates ofethylene oxide with fatty alcohols or with fatty acids or with fattyamines, substituted phenols (preferably alkylphenols or arylphenols),salts of sulphosuccinic esters, taurine derivatives (preferably alkyltaurates), phosphoric esters of polyethoxylated alcohols or phenols,fatty esters of polyols, and derivatives of the compounds containingsulphates, sulphonates and phosphates, for example, alkylaryl polyglycolethers, alkylsulphonates, alkyl sulphates, arylsulphonates, proteinhydrolysates, lignin-sulphite waste liquors and methylcellulose. Thepresence of a surface-active substance is required if one of the activesubstances and/or one of the inert carriers is insoluble in water andwhen the application takes place in water. The proportion ofsurface-active substances is between 5 and 40 percent by weight of thecomposition according to the invention.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide, Prussian blue, and organic dyes, such asalizarin dyes, azo dyes and metal phthalocyanine dyes, and tracenutrients, such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

If appropriate, other additional components may also be present, forexample protective colloids, binders, adhesives, thickeners, thixotropicsubstances, penetrants, stabilizers, sequestring agents, complexformers. In general, the active substances can be combined with anysolid or liquid additive customarily used for formulation purposes.

In general, the formulations contain between 0.05 and 99% by weight,0.01 and 98% by weight, preferably between 0.1 and 95% by weight,especially preferably between 0.5 and 90% by weight of active substance,very especially preferably between 10 and 70 percent by weight.

The active substances or compositions according to the invention can beused as such or, depending on their respective physical and/or chemicalproperties, in the form of their formulations or the use forms preparedtherefrom, such as aerosols, capsule suspensions, cold-foggingconcentrates, warm-fogging concentrates, encapsulated granules, finegranules, flowable concentrates for the treatment of seed, ready-to-usesolutions, dustable powders, emulsifiable concentrates, oil-in-wateremulsions, water-in-oil emulsions, macrogranules, microgranules,oil-dispersible powders, oil-miscible flowable concentrates,oil-miscible liquids, foams, pastes, pesticide-coated seed, suspensionconcentrates, suspoemulsion concentrates, soluble concentrates,suspensions, wettable powders, soluble powders, dusts and granules,water-soluble granules or tablets, water-soluble powders for thetreatment of seed, wettable powders, natural products and syntheticsubstances impregnated with active substance, and alsomicroencapsulations in polymeric substances and in coating materials forseed, and also ULV cold-fogging and warm-fogging formulations.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active substances with at least one customaryextender, solvent or diluent, emulsifier, dispersant and/or binder orfixing agent, wetting agent, water repellant, if appropriate siccativesand UV stabilizers and, if appropriate, dyes and pigments, defoamers,preservatives, secondary thickeners, adhesives, gibberellins and alsofurther processing auxiliaries.

The compositions according to the invention do not only compriseready-to-use compositions which can be applied with suitable apparatusto the plant or the seed, but also commercial concentrates which have tobe diluted with water prior to use.

The active substances according to the invention, per se or in their(commercially available) formulations and in the use forms prepared fromthese formulations, may be present in a mixture with other (known)active substances such as insecticides, attractants, sterilants,bactericides, acaricides, nematicides, fungicides, growth regulators,herbicides, fertilisers, safeners or semiochemicals.

The treatment according to the invention of the plants and plant partswith the active substances or compositions is carried out directly or byaction on their surroundings, habitat or storage space using customarytreatment methods, for example by dipping, spraying, atomizing,irrigating, evaporating, dusting, fogging, broadcasting, foaming,painting, spreading-on, drenching, drip irrigating and, in the case ofpropagation material, in particular in the case of seeds, furthermore bydry seed treatment, by wet seed treatment, by slurry treatment, byincrusting, by coating with one or more coats, etc. It is furthermorepossible to apply the active substances by the ultra-low-volume method,or to inject the active substance preparation, or the active substanceitself, into the soil.

The invention furthermore comprises a method for the treatment of seed.

The invention furthermore relates to seed which has been treated inaccordance with one of the methods described in the previous paragraph.The seeds according to the invention are used in methods for theprotection of seed from undesirable fungi. Here, a seed treated with atleast one active substance according to the invention is used.

The active substances or compositions according to the invention arealso suitable for treating seed. A large part of the damage to cropplants caused by harmful organisms is triggered by the infection of theseed during storage or after sowing as well as during and aftergermination of the plant. This phase is particularly critical since theroots and shoots of the growing plant are particularly sensitive, andeven just small damage may result in the death of the plant.Accordingly, there is great interest in protecting the seed and thegerminating plant by using appropriate compositions.

The control of phytopathogenic fungi by treating the seed of plants hasbeen known for a long time and is the subject of continuousimprovements. However, the treatment of seed entails a series ofproblems which cannot always be solved in a satisfactory manner. Thus,it is desirable to develop methods for protecting the seed and thegerminating plant which dispense with the additional application ofplant protection compositions after sowing or after the emergence of theplants or which at least considerably reduce additional application. Itis furthermore desirable to optimize the amount of active substanceemployed in such a way as to provide maximum protection for the seed andthe germinating plant from attack by phytopathogenic fungi, but withoutdamaging the plant itself by the active substance employed. Inparticular, methods for the treatment of seed should also take intoconsideration the intrinsic fungicidal properties of transgenic plantsin order to achieve optimum protection of the seed and the germinatingplant with a minimum of plant protection compositions being employed.

Accordingly, the present invention also relates to a method forprotecting seed and germinating plants against attack by phytopathogenicfungi by treating the seed with a composition according to theinvention. The invention also relates to the use of the compositionsaccording to the invention for treating seed for protecting the seed andthe germinating plant against phytopathogenic fungi. Furthermore, theinvention relates to seed treated with a composition according to theinvention for protection against phytopathogenic fungi.

The control of phytopathogenic fungi which damage plants post-emergenceis carried out primarily by treating the soil and the above-ground partsof plants with plant protection compositions. Owing to the concernsregarding a possible impact of the plant protection compositions on theenvironment and the health of humans and animals, there are efforts toreduce the amount of active substances applied.

One of the advantages of the present invention is that, because of theparticular systemic properties of the active substances or compositionsaccording to the invention, treatment of the seed with these activesubstances or compositions not only protects the seed itself, but alsothe resulting plants after emergence, from phytopathogenic fungi. Inthis manner, the immediate treatment of the crop at the time of sowingor shortly thereafter can be dispensed with.

It is also considered to be advantageous that the active substances orcompositions according to the invention can be used in particular alsofor transgenic seed where the plant growing from this seed is capable ofexpressing a protein which acts against pests. By treating such seedwith the active substances or compositions according to the invention,even by the expression of the, for example, insecticidal protein,certain pests may be controlled. Surprisingly, a further synergisticeffect may be observed here, which additionally increases theeffectiveness of the protection against attack by pests.

The compositions according to the invention are suitable for protectingseed of any plant variety employed in agriculture, in the greenhouse, inforests or in horticulture and viticulture. In particular, this takesthe form of seed of cereals (such as wheat, barley, rye, triticale,sorghum/millet and oats), maize, cotton, soya beans, rice, potatoes,sunflower, bean, coffee, beet (for example sugar beet and fodder beet),peanut, oilseed rape, poppy, olive, coconut, cacao, sugar cane, tobacco,vegetables (such as tomato, cucumbers, onions and lettuce), turf andornamentals (see also hereinbelow). Of particular importance is thetreatment of the seed of cereals (such as wheat, barley, rye, triticaleand oats), maize and rice.

As also described hereinbelow, the treatment of transgenic seed with theactive substances or compositions according to the invention is ofparticular importance. This refers to the seed of plants containing atleast one heterologous gene which allows the expression of a polypeptideor protein having insecticidal properties. The heterologous gene intransgenic seed can originate, for example, from microorganisms of thespecies Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma,Clavibacter, Glomus or Gliocladium. Preferably, this heterologous geneis from Bacillus sp., the gene product having activity against theEuropean corn borer and/or the Western corn rootworm. Particularlypreferably, the heterologous gene originates from Bacillusthuringiensis.

In the context of the present invention, the composition according tothe invention is applied on its own or in a suitable formulation to theseed. Preferably, the seed is treated in a state in which it issufficiently stable so that the treatment does not cause any damage. Ingeneral, treatment of the seed may take place at any point in timebetween harvesting and sowing. Usually, the seed used has been separatedfrom the plant and freed from cobs, shells, stalks, coats, hairs or theflesh of the fruits. Thus, it is possible to use, for example, seedwhich has been harvested, cleaned and dried to a moisture content ofless than 15% by weight. Alternatively, it is also possible to use seedwhich, after drying, has been treated, for example, with water and thendried again.

When treating the seed, care must generally be taken that the amount ofthe composition according to the invention applied to the seed and/orthe amount of further additives is chosen in such a way that thegermination of the seed is not adversely affected, or that the resultingplant is not damaged. This must be borne in mind in particular in thecase of active substances which may have phytotoxic effects at certainapplication rates.

The compositions according to the invention can be applied directly,that is to say without comprising further components and without havingbeen diluted. In general, it is preferable to apply the compositions tothe seed in the form of a suitable formulation. Suitable formulationsand methods for the treatment of seed are known to the person skilled inthe art and are described, for example, in the following documents: U.S.Pat. No. 4,272,417 A, U.S. Pat. No. 4,245,432 A, U.S. Pat. No. 4,808,430A, U.S. Pat. No. 5,876,739 A, US 2003/0176428 A1, WO 2002/080675 A1, WO2002/028186 A2.

The active substances which can be used according to the invention canbe converted into the customary seed-dressing product formulations suchas solutions, emulsions, suspensions, powders, foams, slurries and othercoating compositions for seed, and ULV formulations.

These formulations are prepared in the known manner by mixing the activesubstances with customary additives such as, for example, customaryextenders and also solvents or diluents, colorants, wetters,dispersants, emulsifiers, antifoams, preservatives, secondarythickeners, adhesives, gibberellins, and also water.

Colorants which may be present in the seed-dressing product formulationswhich can be used according to the invention are all colorants which arecustomary for such purposes. Both pigments, which are sparingly solublein water, and dyes, which are soluble in water, may be used. Examples ofcolorants which may be mentioned are those known by the names RhodaminB, C.I. Pigment Red 112 and C.I. Solvent Red 1.

Wetters which may be present in the seed-dressing product formulationswhich can be used according to the invention are all substances whichare conventionally used for the formulation of agrochemical activesubstances and for promoting wetting. Alkylnaphthalenesulphonates, suchas diisopropyl- or diisobutylnaphthalenesulphonates, can preferably beused.

Suitable dispersants and/or emulsifiers which may be present in theseed-dressing product formulations which can be used in accordance withthe invention are all non-ionic, anionic and cationic dispersants whichare conventionally used for the formulation of agrochemical activesubstances. Non-ionic or anionic dispersants or mixtures of non-ionic oranionic dispersants can preferably be used. Suitable non-ionicdispersants which may be mentioned are, in particular, ethyleneoxide/propylene oxide block polymers, alkylphenol polyglycol ethers andtristryrylphenol polyglycol ethers, and their phosphated or sulphatedderivatives. Suitable anionic dispersants are, in particular,lignosulphonates, polyacrylic acid salts and arylsulphonate/formaldehydecondensates.

Antifoams which may be present in the seed-dressing product formulationswhich can be used according to the invention are all foam-suppressingsubstances conventionally used for the formulation of agrochemicalactive substances. Silicone antifoams and magnesium stearate canpreferably be used.

Preservatives which may be present in the seed-dressing productformulations which can be used according to the invention are allsubstances which can be employed in agrochemical compositions for suchpurposes. Examples which may be mentioned are dichlorophene and benzylalcohol hemiformal.

Secondary thickeners which may be present in the seed-dressing productformulations which can be used according to the invention are allsubstances which can be employed in agrochemical compositions for suchpurposes. Cellulose derivatives, acrylic acid derivatives, xanthan,modified clays and highly disperse silica are preferably suitable.

Adhesives which may be present in the seed-dressing product formulationswhich can be used according to the invention are all customary binderswhich can be employed in seed-dressing products. Polyvinylpyrrolidone,polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned bypreference.

Gibberellins which may be present in the seed-dressing productformulations which can be used according to the invention are preferablythe gibberellins A1, A3 (=gibberellic acid), A4 and A7, with gibberellicacid being particularly preferably used. The gibberellins are known (cf.R. Wegler “Chemie der Pflanzenschutz- and Schädlingsbekämpftmgsmittel”[Chemistry of Plant Protectants and Pesticides], Vol. 2, SpringerVerlag, 1970, pp. 401-412).

The seed-dressing product formulations which can be used in accordancewith the invention can be employed either directly or after previousdilution with water for the treatment of a wide range of seeds,including the seed of transgenic plants. In this context, additionalsynergistic effects may also occur as a consequence of the interactionwith the substances formed by expression.

Suitable apparatuses which can be employed for treating seed with theseed-dressing product formulations which can be used in accordance withthe invention, or with the preparations prepared therefrom by additionof water, are all mixing apparatuses which can usually be employed fordressing seed. Specifically, a seed-dressing procedure is followed inwhich the seed is placed in a mixer, the amount of seed-dressing productformulation desired in each case is added, either as such or afterpreviously diluting it with water, and the contents of the mixer aremixed until the formulation has been distributed uniformly on the seed.If appropriate, this is followed by a drying process.

The active substances or compositions according to the invention have apotent fungicidal activity and can be employed for controlling undesiredfungi in plant protection and in the protection of materials.

The dithiine-tetracarboximides according to the invention can be appliedin plant protection for controlling plasmodiophoromycetes, oomycetes,chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes anddeuteromycetes.

The fungicidal compositions according to the invention can be employedcuratively or protectively for controlling phytopathogenic fungi. Theinvention therefore also relates to curative and protective methods ofcontrolling phytopathogenic fungi by using the active substances orcompositions according to the invention, which are applied to the seed,the plant or plant parts, the fruits or the soil in which the plantsgrow.

The compositions according to the invention for controllingphytopathogenic fungi in plant protection comprise an effective, butnonphytotoxic amount of the active substances according to theinvention. “Effective, but nonphytotoxic amount” means such an amount ofthe composition according to the invention which suffices forsufficiently controlling or fully eradicating the fungal disease of theplant while simultaneously not entailing substantial phytotoxicitysymptoms. In general, this application rate can vary within asubstantial range. It depends on a plurality of factors, for example onthe fungus to be controlled, the plant, the climatic conditions and theconstituents of the compositions according to the invention.

The good plant tolerance of the active substances at the concentrationsrequired for controlling plant diseases permits the treatment of aerialplant parts, of rigiditive propagation material and of seed, and of thesoil.

All plants and plant parts can be treated in accordance with theinvention. In the present context, plants are understood as meaning allplants and plant populations, such as desired and undesired wild plantsor crop plants (including naturally occurring crop plants). Crop plantscan be plants which can be obtained by traditional breeding andoptimization methods or by biotechnological and recombinant methods, orcombinations of these methods, including the transgenic plants andincluding the plant varieties capable or not of being protected by PlantBreeders' Rights. Plant parts are understood as meaning all aerial andsubterranean parts and organs of the plants, such as shoot, leaf, flowerand root, examples which may be mentioned being leaves, needles, stalks,stems, flowers, fruiting bodies, fruits and seeds, and also roots,tubers and rhizomes. The plant parts also include crop material andvegetative and generative propagation material, for example cuttings,tubers, rhizomes, slips and seeds.

The active substances according to the invention are suitable for theprotection of plants and plant organs, for increasing the yields, forimproving the quality of the harvested crop, while being well toleratedby plants, having favourable toxicity to warm-blooded species and beingenvironmentally friendly. They can preferably be employed as plantprotection compositions. They are active against normally sensitive andresistant species and against all or individual developmental stages.

Plants which can be treated in accordance with the invention and whichmay be mentioned are the following: cotton, flax, grapevine, fruit,vegetables, such as Rosaceae sp. (for example pome fruits such as applesand pears, but also stone fruits such as apricots, cherries, almonds andpeaches, and soft fruits such as strawberries), Ribesioidae sp.,Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp.,Moraceae sp., Oleaceae sp., Actimidaceae sp., Lauraceae sp., Musaceaesp. (for example banana plants and banana plantations), Rubiaceae sp.(for example coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (forexample lemons, oranges and grapefruit); Solanaceae sp. (for exampletomatoes), Liliaceae sp., Asteraceae sp. (for example lettuce),Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp.(for example cucumbers), Alliaceae sp. (for example leeks, onions),Papilionaceae sp. (for example peas); major crop plants such asGramineae sp. (for example maize, turf, cereals such as wheat, rye,rice, barley, oats, sorghum, millet and triticale), Asteraceae sp. (forexample sunflower), Brassicaceae sp. (for example white cabbage, redcabbage, broccoli, cauliflower, Brussels sprouts, pak Choi, kohlrabi,small radishes, and also oilseed rape, mustard, horseradish and cress),Fabacae sp. (for example beans, peanuts), Papilionaceae sp. (for examplesoya beans), Solanaceae sp. (for example potatoes), Chenopodiaceae sp.(for example sugar beet, fodder beet, swiss chard, beetroot); usefulplants and ornamentals in gardens and forests; and in each casegenetically modified types of these plants.

As has already been mentioned above, all plants and their parts may betreated in accordance with the invention. In a preferred embodiment,plant species and plant varieties, and their parts, which grow wild orwhich are obtained by traditional biological breeding methods such ashybridization or protoplast fusion are treated. In a further preferredembodiment, transgenic plants and plant varieties which have beenobtained by recombinant methods, if appropriate in combination withtraditional methods (genetically modified organisms), and their partsare treated. The term “parts” or “parts of plants” or “plant parts” hasbeen explained hereinabove. Plants of the plant varieties which are ineach case commercially available or in use are especially preferablytreated in accordance with the invention. Plant varieties are understoodas meaning plants with novel traits which have been bred both bytraditional breeding, by mutagenesis or by recombinant DNA techniques.They may take the form of varieties, races, biotypes and genotypes.

The method of treatment according to the invention can be used in thetreatment of genetically modified organisms (GMOs), e.g. plants orseeds. Genetically modified plants (or transgenic plants) are plants inwhich a heterologous gene has been stably integrated into the genome.The expression “heterologous gene” essentially means a gene which isprovided or assembled outside the plant and when introduced in thenuclear, chloroplastic or mitochondrial genome gives the transformedplant new or improved agronomic or other properties by expressing aprotein or polypeptide of interest or by downregulating or silencingother gene(s) which are present in the plant (using for exampleantisense technology, cosuppression technology or RNAinterference—RNAi—technology). A heterologous gene that is located inthe genome is also called a transgene. A transgene that is defined byits particular location in the plant genome is called a transformationor transgenic event.

Depending on the plant species or plant varieties, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the active substances and compositions which can be usedaccording to the invention, better plant growth, increased tolerance tohigh or low temperatures, increased tolerance to drought or to water orsoil salt content, increased flowering performance, easier harvesting,accelerated maturation, higher harvest yields, bigger fruits, largerplant height, greener leaf colour, earlier flowering, higher qualityand/or a higher nutritional value of the harvested products, highersugar concentration within the fruits, better storage stability and/orprocessability of the harvested products are possible, which exceed theeffects which were actually to be expected.

At certain application rates, the active substance combinationsaccording to the invention may also have a strengthening effect inplants. Accordingly, they are suitable for mobilizing the defense systemof the plant against attack by unwanted phytopathogenic fungi and/ormicroorganisms and/or viruses. This may, if appropriate, be one of thereasons for the enhanced activity of the combinations according to theinvention, for example against fungi. Plant-strengthening(resistance-inducing) substances are to be understood as meaning, in thepresent context, those substances or combinations of substances whichare capable of stimulating the defense system of plants in such a waythat, when subsequently inoculated with unwanted phytopathogenic fungi,the treated plants display a substantial degree of resistance to theseunwanted phytopathogenic fungi. Thus, the substances according to theinvention can be employed for protecting plants against attack by theabovementioned pathogens within a certain period of time after thetreatment. The period of time within which protection is effectedgenerally extends from 1 to 10 days, preferably 1 to 7 days, after thetreatment of the plants with the active substances.

Plants and plant varieties which are preferably to be treated accordingto the invention include all plants which have genetic material whichimparts particularly advantageous, useful traits to these plants(whether obtained by breeding and/or biotechnological means).

Plants and plant varieties which are also preferably to be treatedaccording to the invention are resistant against one or more bioticstresses, i.e. said plants have a better defense against animal andmicrobial pests, such as against nematodes, insects, mites,phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant varieties which may also be treated according to theinvention are those plants which are resistant to one or more abioticstresses. Abiotic stress conditions may include, for example, drought,cold temperature exposure, heat exposure, osmotic stress, waterlogging,increased soil salinity, increased exposure to minerals, exposure toozone, exposure to strong light, limited availability of nitrogennutrients, limited availability of phosphorus nutrients or shadeavoidance.

Plants and plant varieties which may also be treated according to theinvention are those plants characterized by enhanced yieldcharacteristics. Increased yield in said plants can be the result of,for example, improved plant physiology, growth and development, such aswater use efficiency, water retention efficiency, improved nitrogen use,enhanced carbon assimilation, improved photosynthesis, increasedgermination efficiency and accelerated maturation. Yield can furthermorebe affected by improved plant architecture (under stress and non-stressconditions), including early flowering, flowering control for hybridseed production, seedling vigour, plant size, internode number anddistance, root growth, seed size, fruit size, pod size, pod or earnumber, seed number per pod or ear, seed mass, enhanced seed filling,reduced seed dispersal, reduced pod dehiscence and lodging resistance.Further yield traits include seed composition, such as carbohydratecontent, protein content, oil content and composition, nutritionalvalue, reduction in anti-nutritional compounds, improved processabilityand better storage stability.

Plants that may be treated according to the invention are hybrid plantsthat already express the characteristics of heterosis, or hybrid vigour,which results in generally higher yield, vigour, health and resistancetowards biotic and abiotic stress factors. Such plants are typicallymade by crossing an inbred male-sterile parent line (the female parent)with another inbred male-fertile parent line (the male parent). Hybridseed is typically harvested from the male sterile plants and sold togrowers. Male sterile plants can sometimes (e.g. in corn) be produced bydetasseling (i.e. the mechanical removal of the male reproductive organsor male flowers) but, more typically, male sterility is the result ofgenetic determinants in the plant genome. In that case, and especiallywhen seed is the desired product to be harvested from the hybrid plants,it is typically useful to ensure that male fertility in the hybridplants, which contain the genetic determinants responsible for malesterility, is fully restored. This can be accomplished by ensuring thatthe male parents have appropriate fertility restorer genes which arecapable of restoring the male fertility in hybrid plants that containthe genetic determinants responsible for male sterility. Geneticdeterminants for male sterility may be located in the cytoplasm.Examples of cytoplasmic male sterility (CMS) were for instance describedin Brassica species. However, genetic determinants for male sterilitycan also be located in the nuclear genome. Male sterile plants can alsobe obtained by plant biotechnology methods such as genetic engineering.A particularly useful means of obtaining male sterile plants isdescribed in WO 89/10396 in which, for example, a ribonuclease such asbarnase is selectively expressed in the tapetum cells in the stamens.Fertility can then be restored by expression in the tapetum cells of aribonuclease inhibitor such as barstar.

Plants or plant cultivars (obtained by plant biotechnology methods suchas genetic engineering) which may be treated according to the inventionare herbicide-tolerant plants, i.e. plants made tolerant to one or moregiven herbicides. Such plants can be obtained either by genetictransformation, or by selection of plants containing a mutationimparting such herbicide tolerance.

Herbicide-tolerant plants are for example glyphosate-tolerant plants,i.e. plants made tolerant to the herbicide glyphosate or salts thereof.For example, glyphosate-tolerant plants can be obtained by transformingthe plant with a gene encoding the enzyme5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of suchEPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonellatyphimurium, the CP4 gene of the bacterium Agrobacterium sp., the genesencoding a petunia EPSPS, a tomato EPSPS, or an Eleusine EPSPS. It canalso be a mutated EPSPS. Glyphosate-tolerant plants can also be obtainedby expressing a gene that encodes a glyphosate oxidoreductase enzyme.Glyphosate-tolerant plants can also be obtained by expressing a genethat encodes a glyphosate acetyltransferase enzyme. Glyphosate-tolerantplants can also be obtained by selecting plants containing naturallyoccurring mutations of the abovementioned genes.

Other herbicide-resistant plants are for example plants that are madetolerant to herbicides inhibiting the enzyme glutamine synthase, such asbialaphos, phosphinothricin or glufosinate. Such plants can be obtainedby expressing an enzyme detoxifying the herbicide or a mutant glutaminesynthase enzyme that is resistant to inhibition. One such efficientdetoxifying enzyme is, for example, an enzyme encoding aphosphinothricin acetyltransferase (such as the bar or pat protein fromStreptomyces species). Plants expressing an exogenous phosphinothricinacetyltransferase are described.

Further herbicide-tolerant plants are also plants that are made tolerantto the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase(HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze thereaction in which para-hydroxyphenyl pyruvate (HPP) is transformed intohomogentisate. Plants tolerant to HPPD inhibitors can be transformedwith a gene encoding a naturally occurring resistant HPPD enzyme, or agene encoding a mutated HPPD enzyme. Tolerance to HPPD inhibitors canalso be obtained by transforming plants with genes encoding certainenzymes enabling the formation of homogentisate despite the inhibitionof the native HPPD enzyme by the HPPD inhibitor. Tolerance of plants toHPPD inhibitors can also be improved by transforming plants with a geneencoding an enzyme of prephenate dehydrogenase in addition to a geneencoding an HPPD-tolerant enzyme.

Still further herbicide-resistant plants are plants that are madetolerant to acetolactate synthase (ALS) inhibitors. Known ALS inhibitorsinclude, for example, sulphonylurea, imidazolinone, triazolopyrimidines,pyrimidinyloxy(thio)benzoates, and/or sulphonylaminocarbonyltriazolinoneherbicides. Different mutations in the ALS enzyme (also known asacetohydroxyacid synthase, AHAS) are known to confer tolerance todifferent herbicides and groups of herbicides. The production ofsulphonylurea-tolerant plants and imidazolinone-tolerant plants has beendescribed in the international publication WO 1996/033270. Furthersulphonylurea- and imidazolinone-tolerant plants have also beendescribed, for example in WO 2007/024782.

Other plants tolerant to imidazolinone and/or sulphonylurea can beobtained by induced mutagenesis, selection in cell cultures in thepresence of the herbicide or mutation breeding.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are insect-resistant transgenic plants, i.e. plants maderesistant to attack by certain target insects. Such plants can beobtained by genetic transformation, or by selection of plants containinga mutation imparting such insect resistance.

An “insect-resistant transgenic plant”, as used herein, includes anyplant containing at least one transgene comprising a coding sequenceencoding:

1) an insecticidal crystal protein from Bacillus thuringiensis or aninsecticidal portion thereof, such as the insecticidal crystal proteinslisted online at:http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/, or insecticidalportions thereof, e.g. proteins of the Cry protein classes Cry1Ab,Cry1Ac, Cry1F, Cry2Ab, Cry3Ae, or Cry3Bb or insecticidal portionsthereof; or2) a crystal protein from Bacillus thuringiensis or a portion thereofwhich is insecticidal in the presence of a second other crystal proteinfrom Bacillus thuringiensis or a portion thereof, such as the binarytoxin made up of the Cy34 and Cy35 crystal proteins; or3) a hybrid insecticidal protein comprising parts of two differentinsecticidal crystal proteins from Bacillus thuringiensis, such as ahybrid of the proteins of 1) above or a hybrid of the proteins of 2)above, e.g. the Cry1A.105 protein produced by corn event MON98034 (WO2007/027777); or4) a protein of any one of 1) to 3) above wherein some, particularly 1to 10, amino acids have been replaced by another amino acid to obtain ahigher insecticidal activity to a target insect species, and/or toexpand the range of target insect species affected, and/or because ofchanges induced into the encoding DNA during cloning or transformation,such as the Cry3Bb1 protein in corn events MON863 or MON88017, or theCry3A protein in corn event MIR 604; or5) an insecticidal secreted protein from Bacillus thuringiensis orBacillus cereus, or an insecticidal portion thereof, such as thevegetative insecticidal proteins (VIP) listed at:http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/vip.html, e.g.proteins from the VIP3Aa protein class; or6) a secreted protein from Bacillus thuringiensis or Bacillus cereuswhich is insecticidal in the presence of a second secreted protein fromBacillus thuringiensis or B. cereus, such as the binary toxin made up ofthe VIP1A and VIP2A proteins; or7) a hybrid insecticidal protein comprising parts from differentsecreted proteins from Bacillus thuringiensis or Bacillus cereus, suchas a hybrid of the proteins in 1) above or a hybrid of the proteins in2) above; or8) a protein of any one of 1) to 3) above wherein some, particularly 1to 10, amino acids have been replaced by another amino acid to obtain ahigher insecticidal activity to a target insect species, and/or toexpand the range of target insect species affected, and/or because ofchanges induced into the encoding DNA during cloning or transformation(while still encoding an insecticidal protein), such as the VIP3Aaprotein in cotton event COT 102.

Of course, insect-resistant transgenic plants, as used herein, alsoinclude any plant comprising a combination of genes encoding theproteins of any one of the above classes 1 to 8. In one embodiment, aninsect-resistant plant contains more than one transgene encoding aprotein of any one of the above classes 1 to 8, to expand the range oftarget insect species affected or to delay insect resistance developmentto the plants, by using different proteins insecticidal to the sametarget insect species but having a different mode of action, such asbinding to different receptor binding sites in the insect.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are tolerant to abiotic stresses. Such plants can be obtainedby genetic transformation, or by selection of plants containing amutation imparting such stress resistance. Particularly useful stresstolerance plants include:

a. plants which contain a transgene capable of reducing the expressionand/or the activity of the poly(ADP-ribose)polymerase (PARP) gene in theplant cells or plants.b. plants which contain a stress tolerance-enhancing transgene capableof reducing the expression and/or the activity of the PARG-encodinggenes of the plants or plant cells.c. plants which contain a stress tolerance-enhancing transgene codingfor a plant-functional enzyme of the nicotinamide adenine dinucleotidesalvage biosynthesis pathway, including nicotinamidase, nicotinatephosphoribosyltransferase, nicotinic acid mononucleotideadenyltransferase, nicotinamide adenine dinucleotide synthetase ornicotinamide phosphoribosyltransferase.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention show altered quantity, quality and/or storage stability of thecrop product and/or altered properties of specific ingredients of thecrop product such as:

1) transgenic plants which synthesize a modified starch, which in itsphysical-chemical characteristics, in particular the amylose content orthe amylose/amylopectin ratio, the degree of branching, the averagechain length, the side chain distribution, the viscosity behaviour, thegelling strength, the starch grain size and/or the starch grainmorphology, is changed in comparison with the synthesized starch in wildtype plant cells or plants, so that this modified starch is bettersuited for special applications.2) transgenic plants which synthesize non-starch carbohydrate polymersor which synthesize non-starch carbohydrate polymers with alteredproperties in comparison to wild type plants without geneticmodification. Examples are plants which produce polyfructose, especiallyof the inulin and levan type, plants which produce alpha-1,4-glucans,plants which produce alpha-1,6 branched alpha-1,4-glucans, and plantsproducing alternan.3) transgenic plants which produce hyaluronan.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as cotton plants, with altered fibrecharacteristics. Such plants can be obtained by genetic transformation,or by selection of plants containing a mutation imparting such alteredfibre characteristics and include:

-   a) plants, such as cotton plants which contain an altered form of    cellulose synthase genes,-   b) plants, such as cotton plants which contain an altered form of    rsw2 or rsw3 homologous nucleic acids;-   c) plants, such as cotton plants, with an increased expression of    sucrose phosphate synthase;-   d) plants, such as cotton plants, with an increased expression of    sucrose synthase;-   e) plants, such as cotton plants, wherein the timing of the    plasmodesmatal gating at the basis of the fibre cell is altered,    e.g. through downregulation of fibre-selective β-1,3-glucanase;-   f) plants, such as cotton plants, which have fibres with altered    reactivity, e.g. through the expression of the    N-acetylglucosaminetransferase gene including nodC and chitin    synthase genes.

Plants or plant varieties (obtained by plant biotechnology methods suchas genetic engineering) which may also be treated according to theinvention are plants, such as oilseed rape or related Brassica plants,with altered oil profile characteristics. Such plants can be obtained bygenetic transformation or by selection of plants containing a mutationimparting such altered oil characteristics and include:

a) plants, such as oilseed rape plants, which produce oil having a higholeic acid content;b) plants, such as oilseed rape plants, which produce oil having a lowlinolenic acid content;c) plants, such as oilseed rape plants, which produce oil having a lowlevel of saturated fatty acids.

Particularly useful transgenic plants which may be treated according tothe invention are plants which comprise one or more genes which encodeone or more toxins are the following which are sold under the tradenames YIELD GARD® (for example maize, cotton, soya beans), KnockOut®(for example maize), BiteGard® (for example maize), BT-Xtra® (forexample maize), StarLink® (for example maize), Bollgard® (cotton),Nucotn® (cotton), Nucotn 33B® (cotton), NatureGard® (for example maize),Protecta® and NewLeaf® (potato). Examples of herbicide-tolerant plantswhich may be mentioned are maize varieties, cotton varieties and soyabean varieties which are sold under the trade names Roundup Ready®(tolerance to glyphosate, for example maize, cotton, soya beans),Liberty Link® (tolerance to phosphinothricin, for example oilseed rape),IMF® (tolerance to imidazolinone) and SCS® (tolerance to sulphonylurea,for example maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize).

Particularly useful transgenic plants which may be treated according tothe invention are plants containing transformation events, or acombination of transformation events, that are listed for example in thedatabases for various national or regional regulatory agencies (see forexample http://gmoinfo.jrc.it/gmp_browse.aspx andhttp://www.agbios.com/dbase.php).

The active substances or compositions according to the invention mayfurthermore be employed in the protection of materials for protectingindustrial materials against attack and destruction by undesiredmicroorganisms such as, for example, fungi.

In the present context, industrial materials are understood as meaningnonlive materials which have been prepared for use in industry.Industrial materials which are intended to be protected by activesubstances according to the invention from change or destruction byfungi can be, for example, glues, sizes, paper, wall card and board,textiles, carpets, leather, wood, paints and plastic articles, coolinglubricants and other materials which are capable of being attacked ordecomposed by microorganisms. Other materials to be protected and whichcan be adversely affected by the multiplication of microorganisms whichmay be mentioned within the scope are parts of production plants andbuildings, for example cooling water circuits, cooling and heatingsystems and aeration and air-conditioning units. Industrial materialswhich may be mentioned by preference within the scope of the presentinvention are glues, sizes, paper and boards, leather, wood, paints,cooling lubricants and heat-transfer fluids, especially preferably wood.The active substances or compositions according to the invention canprevent disadvantageous effects such as wilting, decay, discolouration,decolouration or mould development. Moreover, the compounds according tothe invention can be employed for protecting objects against beingcovered with growth, in particular ships' hulls, sieves, nets,buildings, jetties and signal units, which come into contact withseawater or brackish water.

The method according to the invention for controlling unwanted fungi canalso be employed for protecting storage goods. Here, storage goods areto be understood as meaning natural substances of vegetable or animalorigin or processed products thereof of natural origin, for whichlong-term protection is desired. Storage goods of vegetable origin, suchas, for example, plants or plant parts, such as stems, leaves, tubers,seeds, fruits, grains, can be protected in the freshly harvested stateor after processing by (pre)drying, moistening, comminuting, grinding,pressing or roasting. Storage goods also include timber, bothunprocessed, such as construction timber, electricity poles andbarriers, or in the form of finished products, such as furniture.Storage goods of animal origin are, for example, pelts, leather, fursand hairs. The active substances according to the invention can preventdisadvantageous effects, such as rotting, decay, discolouration,decolouration or the development of mould.

Some pathogens of fungal diseases which can be treated according to theinvention may be mentioned, by way of example, but not by way oflimitation:

Diseases caused by powdery mildew pathogens, such as, for example,Blumeria species, such as, for example, Blumeria graminis; Podosphaeraspecies, such as, for example, Podosphaera leucotricha; Sphaerothecaspecies, such as, for example, Sphaerotheca fuliginea; Uncinula species,such as, for example, Uncinula necator;Diseases caused by rust disease pathogens, such as, for example,Gymnosporangium species, such as, for example, Gymnosporangium sabinae;Hemileia species, such as, for example, Hemileia vastatrix; Phakopsoraspecies, such as, for example, Phakopsora pachyrhizi and Phakopsorameibomiae; Puccinia species, such as, for example, Puccinia recondita orPuccinia triticina; Uromyces species, such as, for example, Uromycesappendiculatus;Diseases caused by pathogens from the group of the Oomycetes, such as,for example, Bremia species, such as, for example, Bremia lactucae;Peronospora species, such as, for example, Peronospora pisi or P.brassicae; Phytophthora species, such as, for example, Phytophthorainfestans; Plasmopara species, such as, for example, Plasmoparaviticola; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubensis; Pythium species,such as, for example, Pythium ultimum;Leaf blotch diseases and leaf wilt diseases caused, for example, byAlternaria species, such as, for example, Alternaria solani; Cercosporaspecies, such as, for example, Cercospora beticola; Cladiosporumspecies, such as, for example, Cladiosporium cucumerinum; Cochliobolusspecies, such as, for example, Cochliobolus sativus (conidia form:Drechslera, Syn: Helminthosporium); Colletotrichum species, such as, forexample, Colletotrichum lindemuthanium; Cycloconium species, such as,for example, Cycloconium oleaginum; Diaporthe species, such as, forexample, Diaporthe citri; Elsinoe species, such as, for example, Elsinoefawcettii; Gloeosporium species, such as, for example, Gloeosporiumlaeticolor; Glomerella species, such as, for example, Glomerellacingulata; Guignardia species, such as, for example, Guignardiabidwelli; Leptosphaeria species, such as, for example, Leptosphaeriamaculans; Magnaporthe species, such as, for example, Magnaporthe grisea;Microdochium species, such as, for example, Microdochium nivale;Mycosphaerella species, such as, for example, Mycosphaerella graminicolaand M. fijiensis; Phaeosphaeria species, such as, for example,Phaeosphaeria nodorum; Pyrenophora species, such as, for example,Pyrenophora teres; Ramularia species, such as, for example, Ramulariacollo-cygni; Rhynchosporium species, such as, for example,Rhynchosporium secalis; Septoria species, such as, for example, Septoriaapii; Typhula species, such as, for example, Typhula incarnata; Venturiaspecies, such as, for example, Venturia inaequalis;Root and stem diseases caused, for example, by Corticium species, suchas, for example, Corticium graminearum; Fusarium species, such as, forexample, Fusarium oxysporum; Gaeumannomyces species, such as, forexample, Gaeumannomyces graminis; Rhizoctonia species, such as, forexample, Rhizoctonia solani; Tapesia species, such as, for example,Tapesia acuformis; Thielaviopsis species, such as, for example,Thielaviopsis basicola;Ear and panicle diseases (including maize cobs) caused, for example, byAlternaria species, such as, for example, Alternaria spp.; Aspergillusspecies, such as, for example, Aspergillus flavus; Cladosporium species,such as, for example, Cladosporium cladosporioides; Claviceps species,such as, for example, Claviceps purpurea; Fusarium species, such as, forexample, Fusarium culmorum; Gibberella species, such as, for example,Gibberella zeae; Monographella species, such as, for example,Monographella nivalis; Septoria species, such as, for example, Septorianodorum;Diseases caused by smut fungi, such as, for example, Sphacelothecaspecies, such as, for example, Sphacelotheca reiliana; Tilletia species,such as, for example, Tilletia caries, T. controversa; Urocystisspecies, such as, for example, Urocystis occulta; Ustilago species, suchas, for example, Ustilago nuda, U. nuda tritici;Fruit rot caused, for example, by Aspergillus species, such as, forexample, Aspergillus flavus; Botrytis species, such as, for example,Botrytis cinerea; Penicillium species, such as, for example, Penicilliumexpansum and P. purpurogenum; Sclerotinia species, such as, for example,Sclerotinia sclerotiorum;Verticilium species, such as, for example, Verticilium alboatrum;Seed- and soil-borne rot and wilt diseases, and also diseases ofseedlings, caused, for example, by Fusarium species, such as, forexample, Fusarium culmorum; Phytophthora species, such as, for example,Phytophthora cactorum; Pythium species, such as, for example, Pythiumultimum; Rhizoctonia species, such as, for example, Rhizoctonia solani;Sclerotium species, such as, for example, Sclerotium rolfsii;Cancerous diseases, galls and witches' broom caused, for example, byNectria species, such as, for example, Nectria galligena;Wilt diseases caused, for example, by Monilinia species, such as, forexample, Monilinia laxa;Deformations of leaves, flowers and fruits caused, for example, byTaphrina species, such as, for example, Taphrina deformans;Degenerative diseases of woody plants caused, for example, by Escaspecies, such as, for example, Phaemoniella clamydospora andPhaeoacremonium aleophilum and Fomitiporia mediterranea;Diseases of flowers and seeds caused, for example, by Botrytis species,such as, for example, Botrytis cinerea;Diseases of plant tubers caused, for example, by Rhizoctonia species,such as, for example, Rhizoctonia solani; Helminthosporium species, suchas, for example, Helminthosporium solani;Diseases caused by bacteriopathogens, such as, for example, Xanthomonasspecies, such as, for example, Xanthomonas campestris pv. oryzae;Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans; Erwinia species, such as, for example, Erwinia amylovora.

Preference is given to controlling the following diseases of soya beans:

Fungal diseases on leaves, stems, pods and seeds caused, for example, byalternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose(Colletotrichum gloeosporoides dematium var. truncatum), brown spot(Septoria glycines), cercospora leaf spot and blight (Cercosporakikuchii), choanephora leaf blight (Choanephora infundibulifera trispora(Syn.)), dactuliophora leaf spot (dactuliophora glycines), downy mildew(Peronospora manshurica), drechslera blight (Drechslera glycini),frogeye leaf spot (Cercospora sojina), leptosphaerulina leaf spot(Leptosphaerulina trifolii), phyllostica leaf spot (Phyllostictasojaecola), pod and stem blight (Phomopsis sojae), powdery mildew(Microsphaera diffusa), pyrenochaeta leaf spot (Pyrenochaeta glycines),rhizoctonia aerial, foliage, and web blight (Rhizoctonia solani), rust(Phakopsora pachyrhizi, Phakopsora meibomiae), scab (Sphacelomaglycines), stemphylium leaf blight (Stemphylium botryosum), target spot(Corynespora cassiicola). Fungal diseases on roots and the stem basecaused, for example, by black root rot (Calonectria crotalariae),charcoal rot (Macrophomina phaseolina), fusarium blight or wilt, rootrot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras,Fusarium semitectum, Fusarium equiseti), mycoleptodiscus root rot(Mycoleptodiscus terrestris), neocosmospora (Neocosmopspora vasinfecta),pod and stem blight (Diaporthe phaseolorum), stem canker (Diaporthephaseolorum var. caulivora), phytophthora rot (Phytophthora megasperma),brown stem rot (Phialophora gregata), pythium rot (Pythiumaphanidermatum, Pythium irregulare, Pythium debaryanum, Pythiummyriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, anddamping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotiniasclerotiorum), sclerotinia Southern blight (Sclerotinia rolfsii),thielaviopsis root rot (Thielaviopsis basicola).

Organisms which can bring about degradation or modification of theindustrial materials and which may be mentioned are fungi. The activesubstances according to the invention are preferably active againstfungi, in particular moulds, wood-discolouring and wood-destroying fungi(Basidiomycetes). Fungi of the following genera may be mentioned by wayof example: Alternaria, such as Alternaria tenuis; Aspergillus, such asAspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora,such as Coniophora puetana; Lentinus, such as Lentinus tigrinus;Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporusversicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma,such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride.

Moreover, the active substances according to the invention also havevery good antimycotic activities. They have a very broad antimycoticspectrum of action, in particular against dermatophytes and spreadingfungi, mould and diphasic fungi (for example against Candida speciessuch as Candida albicans, Candida glabrata) and against Epidermophytonfloccosum, Aspergillus species such as Aspergillus niger and Aspergillusfumigatus, Trichophyton species such as Trichophyton mentagrophytes,Microsporon species such as Microsporon canis and audouinii. Theenumeration of these fungi on no account constitutes a limitation of themycotic spectrum which can be controlled, but only has illustrativecharacter.

When employing the active substances according to the invention asfungicides, the application rates may vary within a substantial range,depending on the type of application. The application rate of the activesubstances according to the invention is

-   -   when treating plant parts, for example leaves: from 0.1 to 10        000 g/ha, preferably from 10 to 1000 g/ha, particularly        preferably from 50 to 300 g/ha (when the application is carried        out by watering or dropwise, it may even be possible to reduce        the application rate, in particular when inert substrates such        as rock wool or perlite are used);    -   when treating seed: from 2 to 200 g per 100 kg of seed,        preferably from 3 to 150 g per 100 kg of seed, especially        preferably from 2.5 to 25 g per 100 kg of seed, very especially        preferably from 2.5 to 12.5 g per 100 kg of seed;    -   when treating the soil: from 0.1 to 10 000 g/ha, preferably from        1 to 5000 g/ha.

These application rates are mentioned only by way of example and not byway of limitation in the sense of the invention.

The active substances or compositions according to the invention canthus be employed for protecting plants for a certain period of timeafter treatment against attack by the pathogens mentioned. The periodfor which protection is provided extends generally for 1 to 28 days,preferably 1 to 14 days, particularly preferably 1 to 10 days, veryparticularly preferably 1 to 7 days after the treatment of the plantswith the active substances, or up to 200 days after the treatment ofseed.

In addition, by the treatment according to the invention it is possibleto reduce the mycotoxin content in the harvested material and thefoodstuff and feedstuff prepared therefrom. Particular, but notexclusive, mention may be made here of the following mycotoxins:deoxynivalenol (DON), nivalenol, 15-Ac-DON, 3-Ac-DON, T2- and HT2-toxin,fumonisine, zearalenon, moniliformin, fusarin, diaceotoxyscirpenol(DAS), beauvericin, enniatin, fusaroproliferin, fusarenol, ochratoxins,patulin, ergot alkaloids and aflatoxins produced, for example, by thefollowing fungi: Fusarium spec., such as Fusarium acuminatum, F.avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberellazeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F.proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi,F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F.subglutinans, F. tricinctum, F. verticillioides, inter alia, and also byAspergillus spec., Penicillium spec., Claviceps purpurea, Stachybotrysspec. inter alia.

The abovementioned plants can be treated especially advantageously inaccordance with the invention with the compounds of the general formula(I) or with dithiine-diisoimides of the formula (V) or with thecompositions according to the invention. The preferred ranges indicatedabove for the active substances or compositions also apply to thetreatment of these plants. The treatment of plants with the compounds orcompositions mentioned specifically in the present text should beespecially emphasised.

PREPARATION EXAMPLES Preparation of2,6-bis[1-(trifluoromethyl)cyclopropyl]-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone[compound No. (7)]

Slowly, 7.57 ml (103.75 mmol) of thionyl chloride were added dropwise toa solution of 0.8 g (3.55 mmol) of4-oxo-4-{[1-(trifluoromethyl)cyclopropyl]amino}butanoic acid (IV-1) in 2ml of dioxane, with ice-cooling (15° C.). The mixture was allowed towarm to room temperature overnight, and the solution was concentrated.The residue is poured onto ice, extracted with ethyl acetate, dried andconcentrated. After chromatography on silica gel (cyclohexane/ethylacetate 1:1), 284 mg (34% of theory) of the desired compound wereobtained.

Preparation of(1,3,5,7-tetraoxo-1,3,5,7-tetrahydro-2H,6H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-2,6-diyl)dipropane-1,2-diyldiacetate [compound No. (36)]

To a solution of 1.1 g (3.72 mmol) of1-(3,4-dichloro-2,5-dioxo-2,5-dihydro-1H-pyrrol-1-yl)propan-2-yl acetatein 10 ml of ethanol, there was added 0.283 g (3.72 mmol) of thiourea,and stirring was continued for 5 hours at 40° C. After the mixture hascooled to room temperature, green crystals were filtered off withsuction and rinsed with water/ethanol. The filtrate was extracted withwater and ethyl acetate, dried and concentrated. The mother liquor waschromatographed on silica gel (cyclohexane/ethyl acetate gradient0%-100%). This gave 0.334 g (39.5% of theory) of the desired compound.

Preparation of2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone4-oxide [compound No. (38)]

With stirring, 3 g (10.63 mmol) of2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone[compound No. (1)] were added to 20 ml of ice-cooled (5° C.) fumingnitric acid. After dissolution was complete, stirring was continued for5 min, the mixture was subsequently poured into ice-water and the yellowcrystals were filtered off with suction. This gave 2.56 g (80.8% oftheory) of the desired compound.

The compounds of the formula (I) which are mentioned in Table 1hereinbelow can be obtained analogously to the above examples and inaccordance with the general descriptions of the processes.

TABLE 1 (I)

No. R¹ R² n Physical data 1 Me Me 0 log P = 2.32 2 Et Et 0 ¹H NMR (400MHz, DMSO-d₆): δ = 1.096; 3.442 ppm 3 nPr nPr 0 ¹H NMR (400 MHz,DMSO-d₆): δ = 0.822; 1.566; 3.362 ppm 4 iPr iPr 0 log P = 4.19 5 cPr cPr0 ¹H NMR (400 MHz, DMSO-d₆): δ = 0.50-0.89 ppm 6 —CH₂CF₃ —CH₂CF₃ 0 log P= 3.41 7 1-(trifluoromethyl)- 1-(trifluoromethyl)- 0 log P = 4.03cyclopropyl cyclopropyl 8 H H 0 log P = 1.13 9 3,5-dichlorophenyl3,5-dichlorophenyl 0 m.p. > 300° C. 10 Ph Ph 0 m.p. > 300° C. 11 Bz Bz 0log P = 4.60 12 2-methoxyethyl 2-methoxyethyl 0 log P = 2.55 132-hydroxybutyl 2-hydroxybutyl 0 log P = 2.27 14 2-hydroxypropyl2-hydroxypropyl 0 log P = 1.63 15 2-phenoxyethyl -phenoxyethyl 0 log P =3.86 16 2-ethoxyethyl 2-ethoxyethyl 0 log P = 3.24 172-phenylpropan-2-yl 2-phenylpropan-2-yl 0 ¹H NMR (400 MHz, DMSO-d₆): δ =7.20-7.35 ppm 18 1-phenylethyl 1-phenylethyl 0 ¹H NMR (400 MHz,DMSO-d₆): δ = 5.197; 5.215; 5.234; 5.251 ppm 19 2-methoxy-2-2-methoxy-2- 0 methylpropyl methylpropyl 20 tBu tBu 0 21—(CH₂)₂OC(═O)CH₃ —(CH₂)₂OC(═O)CH₃ 0 ¹H NMR (400 MHz, DMSO-d₆): δ =1.053; 3.654; 4.110 ppm 22

0 ¹H NMR (400 MHz, DMSO-d₆): δ = 7.492; 7.596; 7.583; 7.946; 7.966 ppm23 —CH₂CO₂H —CH₂CO₂H 0 ¹H NMR (400 MHz, DMSO-d₆): δ = 4.166 ppm 24

0 log P = 1.76 25

0 26

0 27

0 ¹H NMR (400 MHz, DMSO-d₆): δ = 1.620 ppm 28

0 log P = 1.99 29 —(CH₂)₄CO₂H —(CH₂)₄CO₂H 0 log P = 2.02 303-(trifluoromethyl)- 3-(trifluoromethyl)- 0 ¹³C NMR (150 MHz, DMSO-d₆):δ = 23.01; cyclohexyl cyclohexyl 23.71; 27.85; 28.61; 49.19; 126.77;128.62; 130.56; 164.22 ppm 31 3-(trifluoromethyl)- 3-(trifluoromethyl)-0 log P = 4.91 phenyl phenyl 32

0 log P = 3.12 33 2-hydroxyethyl 2-hydroxyethyl 0 ¹H NMR (400 MHz,DMSO-d₆): δ = 3.480 ppm 34 2-hydroxy-2- 2-hydroxy-2- 0 log P = 3.65methylpropyl methylpropyl 35

0 log P = 3.09 36

0 log P = 3.09 37 hydroxymethyl hydroxymethyl 0 ¹H NMR (400 MHz,DMSO-d₆): δ = 3.135; 4.789 ppm 38 Me Me 1 m.p. 205° C. 39 H Et 0 log P =2.13 40

0 log P = 4.66 41

0 log P = 1.73 Me = methyl, Et = ethyl, nPr = n-propyl, iPr = isopropyl,cPr = cyclopropyl, tBu = tert-butyl, Bz = benzyl, Ph = phenyl

Preparation of Starting Materials of the Formula (Iv) Preparation of4-oxo-4-{[1-(trifluoromethyl)cyclopropyl]amino}butanoic acid (IV-1)

Slowly, 800.7 mg (4.96 mmol) of 1-(trifluoromethyl)cyclopropanamine and0.85 ml (4.96 mmol) of diisopropylethylamine were added to a solution of496 mg (4.96 mmol) of succinic anhydride in 10 ml of dioxane, withice-cooling (10° C.). Stirring was continued for 20 min at roomtemperature, and the mixture was allowed to stand overnight at thistemperature. Again, stirring was continued for 20 min at 80° C., themixture was allowed to cool to room temperature, and the solution wasconcentrated. Repeatedly, the solution was washed alternately with ethylacetate and with water. The combined organic phases were dried andconcentrated. This gave 815.8 mg (73% of theory) of the desiredcompound.

The determination of the logP values detailed in the tables andpreparation examples hereinabove is carried out in accordance with EECDirective 79/831 Annex V.A8 by means of HPLC (High Performance LiquidChromatography) on a reversed-phase column (C 18). Temperature: 43° C.

The determination is carried out in the acidic range at pH 2.7, using0.1% strength aqueous formic acid and acetonitrile (contains 0.1% formicacid) as eluents; linear gradient from 10% acetonitrile to 95%acetonitrile.

Calibration is carried out using unbranched alkan-2-ones (with 3 to 16carbon atoms) with known logP values (determination of the logP valueswith reference to the retention times by linear interpolation betweentwo successive alkanones).

USE EXAMPLES Example A Phytophthora Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To prepare a suitable preparation of active substance, 1 part by weightof active substance is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive substance preparation at the application rate detailed. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Phytophthora infestans. Then, the plants are placedinto an incubation cabinet at approximately 20° C. and 100% relativeatmospheric humidity. Evaluation is carried out 3 days after theinoculation. 0% means an efficacy which corresponds to that of thecontrol, while an efficacy of 100% means that no disease is observed.

In this test, the compounds 1, 2 and 3 according to the invention showedan efficacy of 70% or more at an active substance concentration of 250ppm.

Example B Plasmopara Test (Grapevine)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To prepare a suitable preparation of active substance, 1 part by weightof active substance is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive substance preparation at the application rate detailed. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Plasmopara viticola and then remain for 1 day in anincubation cabinet at approximately 20° C. and 100% relative atmospherichumidity. Thereafter, the plants are placed for 4 days in the greenhouseat approximately 21° C. and approximately 90% atmospheric humidity. Theplants are then moistened and placed for 1 day into an incubationcabinet. Evaluation is carried out 6 days after the inoculation. 0%means an efficacy which corresponds to that of the control, while anefficacy of 100% means that no disease is observed.

In this test, the compounds 1, 2 and 3 according to the invention showedan efficacy of 70% or more at an active substance concentration of 250ppm.

Example C Venturia Test (Apple)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To prepare a suitable preparation of active substance, 1 part by weightof active substance is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive substance preparation at the application rate detailed. After thespray coating has dried on, the plants are inoculated with an aqueousconidia suspension of the apple scab pathogen Venturia inaequalis andthen remain for 1 day in an incubation cabinet at approximately 20° C.and 100% relative atmospheric humidity. Thereafter, the plants areplaced in the greenhouse at approximately 21° C. and approximately 90%relative atmospheric humidity. Evaluation is carried out 10 days afterthe inoculation. 0% means an efficacy which corresponds to that of thecontrol, while an efficacy of 100% means that no disease is observed.

In this test, the compounds 1, 2 and 3 according to the invention showedan efficacy of 70% or more at an active substance concentration of 250ppm.

Example D Alternaria Test (Tomato)/Protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight ofdimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycolether

To prepare a suitable preparation of active substance, 1 part by weightof active substance is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive substance preparation at the application rate detailed. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Alternaria solani. Then, the plants are placed intoan incubation cabinet at approximately 20° C. and 100% relativeatmospheric humidity. Evaluation is carried out 3 days after theinoculation. 0% means an efficacy which corresponds to that of thecontrol, while an efficacy of 100% means that no disease is observed.

In this test, the compounds 1, 2 and 3 according to the invention showedan efficacy of 70% or more at an active substance concentration of 250ppm.

Example E Botrytis Test (Cucumber)/Protective

Solvent: 49 parts by weight of N,N-dimethylformamide Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active substance, 1 part by weightof active substance is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young cucumber plants are sprayed withthe active substance preparation at the application rate detailed. Oneday after the treatment, the plants are inoculated with a sporesuspension of Botrytis cinerea and are then left to stand for 48 h at100% relative humidity at 22° C. Thereafter, the plants are left tostand at 96% relative atmospheric humidity and a temperature of 14° C.Evaluation is carried out 5-6 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of100% means that no disease is observed.

In this test, the compounds 1, 2 and 3 according to the invention showedan efficacy of 70% or more at an active substance concentration of 500ppm.

Example F Pyrenophora teres Test (Barley)/Protective

Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 partby weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active substance, 1 part by weightof active substance is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with theactive substance preparation at the application rate detailed. After thespray coating has dried on, the plants are sprayed with a sporesuspension of Pyrenophora teres. The plants remain in an incubationcabinet for 48 hours at 20° C. and 100% relative atmospheric humidity.The plants are placed in a greenhouse at a temperature of approximately20° C. and a relative atmospheric humidity of approximately 80%.

Evaluation is carried out 8 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of100% means that no disease is observed.

In this test, the compound I according to the invention showed anefficacy of 70% or more at an active substance concentration of 1000ppm.

1. Use of dithiine-tetracarboximides of the general formula (I)

in which R¹ and R² are identical or different and represent hydrogen,C₁-C₈-alkyl which is optionally monosubstituted or polysubstituted byhalogen, —OR³, —COR⁴, or represent C₃-C₇-cycloalkyl which are optionallymonosubstituted or polysubstituted by halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, or represent aryl or aryl-(C₁-C₄-alkyl), each of whichis optionally monosubstituted or polysubstituted by halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, —COR⁴ or sulphonylamino, R³ representshydrogen, C₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or represents aryl which isoptionally monosubstituted or polysubstituted by halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, R⁴ represents hydroxyl, C₁-C₄-alkyl or C₁-C₄-alkoxy, nrepresents 0 or 1 for controlling phytopathogenic fungi.
 2. Useaccording to claim 1, characterized in that R¹ and R² are identical ordifferent and represent hydrogen, or represent C₁-C₆-alkyl which isoptionally monosubstituted or polysubstituted by fluorine, chlorine,bromine, —OR³, —COR⁴, or represent C₃-C₇-cycloalkyl which is optionallymonosubstituted or polysubstituted by chlorine, methyl ortrifluoromethyl, or represent phenyl or phenyl-(C₁-C₄-alkyl), each ofwhich is optionally monosubstituted or polysubstituted by fluorine,chlorine, bromine, methyl, trifluoromethyl, —COR⁴, sulphonylamino, R³represents hydrogen, methyl, ethyl, methylcarbonyl, ethylcarbonyl orrepresents phenyl which is optionally monosubstituted or polysubstitutedby fluorine, chlorine, methyl, ethyl, n-propyl, isopropyl ortrifluoromethyl, R⁴ represents hydroxyl, methyl, ethyl, methoxy orethoxy, n represents 0 or
 1. 3. Use according to claim 1, characterizedin that R¹ and R² are identical or different and represent hydrogen, orrepresent C₁-C₄-alkyl which is optionally monosubstituted orpolysubstituted by fluorine, chlorine, hydroxyl, methoxy, ethoxy,methylcarbonyloxy, carboxyl, or represent C₃-C₇-cycloalkyl which isoptionally monosubstituted or polysubstituted by chlorine, methyl ortrifluoromethyl, or represent phenyl, benzyl, 1-phenethyl, 2-phenethylor 2-methyl-2-phenethyl, each of which is optionally monosubstituted totrisubstituted by fluorine, chlorine, bromine, methyl, trifluoromethyl,—COR⁴, sulphonylamino, R³ represents hydrogen, methyl, methylcarbonyl orphenyl, R⁴ represents hydroxyl or methoxy, n represents 0 or
 1. 4. Useaccording to claim 1, characterized in that R¹ and R² simultaneouslyrepresent methyl.
 5. Composition for controlling phytopathogenic fungi,characterized in that it contains at least one dithiine-tetracarboximideof the formula (I) according to claim 1, besides extenders and/orsurface-active substances.
 6. Method of controlling phytopathogenicfungi, characterized in that dithiine-tetracarboximides of the formula(I) according to claim 1 are applied to the fungi and/or theirenvironment.
 7. Dithiine-tetracarboximides of the formula (I-a)

in which R^(1a) and R^(2a) are identical or different and representC₁-C₈-alkyl which is monosubstituted or polysubstituted by fluorine,—OR^(3a), —COR^(4a), or represent C₃-C₇-cycloalkyl which is optionallymonosubstituted or polysubstituted by halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, or represent aryl-(C₁-C₄-alkyl) which ismonosubstituted in the alkyl moiety by —COR^(4a), R^(3a) representsC₁-C₄-alkyl, C₁-C₄-alkylcarbonyl, or represents aryl which is optionallymonosubstituted or polysubstituted by halogen, C₁-C₄-alkyl orC₁-C₄-haloalkyl, R^(4a) represents hydroxyl, C₁-C₄-alkyl orC₁-C₄-alkoxy, r represents 0 or 1, where R^(1a) and R^(2a)a do notsimultaneously represent acetoxymethyl or methoxymethyl. 8.Dithiine-tetracarboximides of the formula (I-a) according to claim 8, inwhich R^(1a) and R^(2a) are identical or different and representC₁-C₆-alkyl which is monosubstituted or polysubstituted by fluorine,—OR^(3a), —COR^(4a), or represent C₃-C₇-cycloalky which is optionallymonosubstituted or polysubstituted by chlorine, methyl ortrifluoromethyl, or represent phenyl-(C₁-C₄-alkyl) which ismonosubstituted in the alkyl moiety by —COR^(4a), R^(3a) representsmethyl, ethyl, methylcarbonyl, ethylcarbonyl, or represents phenyl whichis optionally monosubstituted or polysubstituted by fluorine, chlorine,methyl, ethyl, n-propyl, isopropyl or trifluoromethyl, R^(4a) representshydroxyl, methyl, ethyl, methoxy or ethoxy, r represents 0 or 1, whereR^(1a) and R^(2a) do not represent acetoxymethyl. 9.Dithiine-tetracarboximides of the formula (I-a) according to claim 8 or9, in which R^(1a) and R^(2a) are identical or different and representC₁-C₄-alkyl which is monosubstituted or polysubstituted by fluorine,hydroxyl, methoxy, ethoxy, methylcarbonyloxy, carboxyl, or representC₃-C₇-cycloalkyl which is optionally monosubstituted or polysubstitutedby chlorine, methyl or trifluoromethyl, or represent 1-phenethyl or2-phenethyl, each of which is monosubstituted in the alkyl moiety by—COR^(4a), R^(3a) represents methyl, methylcarbonyl or phenyl, R^(4a)represents hydroxyl or methoxy, r represents 0, where R^(1a) and R^(2a)a do not represent acetoxymethyl.
 10. Use of dithiine-diisoimides of theformula (V)

in which R¹ and R² have the meanings given in claim 1 for controllingphytopathogenic fungi.
 11. Dithiine-diisoimides of the formula (V-a)

in which R^(1a) and R^(2a) have the meanings given in claim 7.